Haloglycoluril bactericidal compositions for disinfecting and bleaching



fll jfifi Patented Jan. 30, 1962 3,019,160 HALOGLYCOLURIL BACTERICIDAL COMPOSI- TIONS FDR DI1NFECTING AND BLEACI-HNG Frank B. Slezak and Irving Rosen, Painesville, Ohio, as-

signors to Diamond Alkali Company, Cleveland, Qhio,

a corporation of Delaware No Drawing. Filed May 11, 1959, Ser. No. 812,133

11 Claims. (Cl. 167-33) This invention relates to novel haloglycolurils and more particularly relates to the polyhaloglycolurils of the following structure:

Specific illustrative compounds embodying this invention are:

2,4,6,8 tetrachloro 2,4,6,8 tetrazabicyclo(3.3.0)octa-3,

1,5-dimethyl 2,4,6,8 tetrachloro-2,4,6,8-tetrazabicyclo- (3.3.1)nona-3,7-dione (I31 (3H3 $1 in :0 CH; C=O l t l I l 1 Cl CH3 Cl Dichloro 2,4,6,8 tetrazabicyclo(3.3.0)octa-3,7-dione Compounds of this invention have a high available chlorine content and are characterized by a single activity as bleaches, sanitizers, i.e., in applications wherein the compound employed reduces the number of microorganisms on an inanimate object or surface to a safe level, and in disinfecting and bactericidal applications generally, as Well as in verious biologically active compositions such as fungicides and nematocides. Of particular interest is the novel compounds comprising line materials serve to provide a desirable pH at which the compounds are often more soluble and in many instances.

bleaching and sanitizing activity of compounds of this invention which is further enhanced by the fact that compounds of this invention generally are solids and thus inherently provide a significant improvement over many prior conventional bleaching and sanitizing agents including the well-known and widely used sodium hypochlorite solution. Moreover, the fact that compounds of this invention are solids provides increased convenience by way of easier handling, reduced likelihood of incurring damage by breakage, freezing or spilling.

Moreover, compounds of this invention generally are characterized by excellent stability so that their activity is not significantly reduced on storage although in some instances, these compounds appear somewhat less stable after extended storage in the presence of alkaline materials under conditions wherein chemical reaction therewith can occur.

Compounds of this invention generally may be prepared by halogenating a glycoluril or an alkyl-substituted glycoluril desirably in an alkaline aqueous solution rendered alkaline by addition of an alkali metal carbonate, e.g., sodium carbonate, alkali metal bicarbonate, e.g., sodium bicarbonate, or alkali metal hydroxide, e.g., sodium hydroxide, alkali metal borates, e.g., sodium borate, a1- kali meal silicates, e.g., sodium metasilicate, preferably an alkali metal carbonate, all as will be described more specifically hereinafter.

It is also a specific feature of this invention that compounds of the foregoing type are advantageously em ploycd, not only singly, but in admixture wherein in many instances a synergistic effect is observed insofar as bleaching and sanitizing activity is concerned.

One of the most advantageous applications of compounds of this invention is in compositions useful in bleaching, sterilizing, bacterial toxicant, and detergent applications. Hence, it will be understood that compounds of this invention are useful when mixed with water and in certain instances with other liquids to yield materials suit-' sterilizing and disinfecting such as in able for bleaching, the treatment of food containers, e.g., metal and other type containers used in the transport of food products such as milk, cream and the like, as well as in oxidizing type'detergents. for use in hospitals and other places such as hotels" and restaurants for dishwashing and the like where a high available chlorine content is deproduct having a sirable.

Accordingly,

as ingredients in compositions which also contain a major,

or minor, although usually a major proportion, of other salts such as alkali metal carbonates, silictes, phosphates" and the like, e.g., sodium or potassium carbonates, bicarbonates, silicates, phosphates and the like. The'alkaalso provides advantageous detergent or washing properties in solution.

In this connection, it will be appreciated that various alkaline phosphates including alkali metal phosphates and alkaline earth metal phosphates useful in detergent compositions such as sodium tripolyphosphates, sodium pyrophosphates, trisodium phosphates and the like, may be incorporated into compositions advantageously including also one or more compounds of this invention. Similarly, it will be understood that the various alkaline silicates, notably alkali metal silicates such as alkali metal metasilicates as well as those silicates having an alkali metal oxide: silicon dioxide ratio within the range from about 2.1:1.0

in view of the variety of advantageous I applications of compounds of this invention, it will be un-' derstood that the novel haloglycolurils may be employed to ,l.0:3.3, may be utilized, e.g., sodium silicate having Na O:SiO ratios within the range from 2.0Na 0:1.0SiO to 1.0Na 0:3.3SiO

In addition to these detergent ingredients, it will be further understood that various organic wetting agents such as alkyl aryl sulfonates, e.g., sodium dodecyl benzene sulfonate, alkyl phenoxyethylene alkanols, aikyl aryl polyether alcohol, or other wetting agents or surface-active materials may be included as well as soaps, fillers, abrasives and water softening agents of organic or inorganic type incorporated as desired to provide specific properties required in a particular application.

Further, it will be appreciated that compositions of this invention particularly adapted in the sterilization, disinfectant, bleaching and detergent applications may either be dry particulate materials ranging from finely-divided powders to granular materials of increased particle size to pastes and liquid slurries and/or solutions, depending on the application intended.

It will be appreciated, of course, that in the variety of applications contemplated for compounds of this invention the proportions of these compounds with respect to the other ingredients employed can be varied. However, it may be stated that in many applications the novel haloglycolurils of this invention desirably will comprise minor amounts of about 1% by weight or less, up to about based on the total composition employed, frequently in amounts constituting a small but effective quantity appreciably less than 1%, up to a much greater proportion dictated by a number of factors including cost, application, equipment and other considerations, e.g., as high as 100% in certain instances where the pure material is advantageously utilized.

In other applications, for example, in which the com pounds of this invention advantageously are utilized as biologically active substances, somewhat similar considerations obtain, i.e., compounds of: this invention may be utilized in biologically active compositions in which they constitute but a minor amount of the total composition,

e.g., there may be employed as essential ingredients in various compositions including a rnajor proportion of one or more diluents, extenders, fillers, conditioners, solvents or 'the like such as various dry materials including clay, diatomaceous earth, talc, spent catalyst, alumina silica material s, silica and the like, as well as liquids such as water and various organic liquids such as acetone, kerosene, ben:zene toluene, xylene and other petroleum distillate fractions, isomers or mixtures thereof.

When liquidformulatious are employed or dry materialsprepared are to be used in liquid form, it is desirable in certain instances, as in the case of compositions useful'insterilizing, disinfectingbleaching and detergent appliCatiOnsQto employ a wetting, dispersing, or other surface-active agent to I Accordingly, the term '.carrier as employed throughnature specification and claims is intended to refer broad ly tothe material or materials constituting a major proportion of a biologically active or other formulation and hence includes finely divided materials, both liquids and Solid 'as aforementioned, conventionally used in such an application. p 7 I ;In order that those skilled in the art may more cornpletely understand the present invention and the preferred methods by which the same may be carried intoeffect, the'foll'owing specific'examples are offered:

EXAMPLE r Part 7A" of glycoluril. Theresultahtmixture is chlorina'ted while facilitate use of the formulation.

' The resultant material continuously being agitated, sodium bicarbonate solution (150 gms. sodium bicarbonate in 2 liters of water) being added at a rate to maintain the pH of the solution between 4 and 8. Chlorination is continued until 130% of the stoichiometric amount of chlorine is introduced, i.e., a

total of 182 gms. The resultant solid is separated, washed Part B There are added to300 ml. of water 8l0 gIri s."(0'.094 mol) sodium bicarbonate and 2.8 gms. (0.02 mol) glycoluril. This mixture is heated to 50-55 C. and has an initial pH of 8.0. Chlorination is then begun (pH 8.0) and is continued to a pH of 3.3. The resultant white solid is separated, washed with 75 m1. of water,

filtered again and allowed to dry under suction. Chemical analysis indicates preparation of the desired C H Cl N O and is as follows:

Element Percent Percent calculated actual 17.16 17.47 0.72 0. 50.67 50. N 20.02 20. Available chlorin 101; 4 98.

EXAMPLE II PREPARATION OF D1cHLoRo-2,4,6,s@ETRAZABICYCLO' (3.3.0)OCTA-3,7-DIONE There is suspended in 800 ml. of water 14.2 gms. (0.1 mol) of glycoluril and the introduction of chlorine is egun, a 6 N solution of NaOI-I'being added portionwise to maintain the pH within the range from 7 to 8. A total of 89.2% of the'theoretical amount of chlorine (based on stoichiometric amount required to form trichloroglycoluril), and 45 ml. of 6 N N'aOH introduced.

is filtered and the filtnate evaporated to dryness to yield 34.8 gms. of a white solid. This solid is'washed twice with water and driedimder's'uction. There results 17.1 gms. of a white solid. Chemical analysis indicates preparation of the desired C H Cl N O and is as follows:

Element Percent Percent calculated actual 22. 76 22. 40 1. 91 1. 56 33. 63 35. 1 N 26. 54 25. 95 Available chlorine 68. 08 69.1

is then gradually introduced into the. stirred solution simultaneously :with the addition of 6 N sodium hydroxide .at' a rate to maintain the pH' of within the range from approximately-5 to 8. 'A total of of the theoretical amount ofchlorine' (-1l0 gms.)

and 125 %"of the theoretical amount of6N'sodiu'rn'hydroxide (250.2 ml.) fareadded. Theresultant reaction PENN) the-reaction mixture mixture is filtered and the pasty residue washed with 400 to 600 ml. of water and filtered again. The thus-obtained solid is allowed to dry to yield a White powder Weighing 86.8 gms. Chemical analysis indicates that it contains 78.3% available chlorine (theoretical available chlorine 88%). Chemical analysis indicates perparation of the desired C H CI N O and is as follows:

Element Percent Percent actual calculated 0. 27. 49 26. 10 H 2. 51 2. 50 Cl 40. 3 44. 08 N- 18.19 17.39

Bleaching effectiveness of compounds of this invention:

EXAMPLE IV Part A To illustrate the effectiveness of compounds of this invention as bleaching agents tests are conducted whereby tea-stained, unbleached muslin is bleached in solutions containing such compounds. More particularly, the procedure employed is as follows:

Unbleached muslin is scoured for six hours at the boil in nine liters of a 1% NaOH solution containing gins. of Nacconal NR (alkyl aryl sulfonate) and 2.0 grns. of Rapidase-Z (starch and size-removing bacteria). The thus-scoured muslin (465 grns.) is then stained by immersion in a solution consisting of nine liters of Water containing 140 ml. of a stock tea solution prepared by leaching 15 conventional tea bags in one liter of water for minutes at 97 C. The thus-treated cloth is then rinsed in cold water and dried.

Bleach baths are prepared by adding suflicient of a saturated aqueous solution of the compound being investigated to provide a bath 300 ml. in volume and containing 100 p.p.m. of available chlorine, using a 5% aqueous solution of sodium tripolyphosphate to buffer the bath to a pH of about 9.4. The available chlorine content is checked just prior to conducting the tests by titration against sodium thiosulphate using starch as an indicator.

Using such bleach solutions in glass jars, one strip (9 x 7 inches) of unbleached, scoured, tea-stained muslin is immersed in each bath and the jar placed in the water bath of a Launder-Orneter (Atlas Electric Devices Company) (Model B-S, Type LHD-EF) for twenty minutes at a predetermined test temperature. The muslin is then washed with cold tap water, dried, and the bleach effectiveness determined by measuring the reflectance of the bleached samples with a refiectometer (Hunter Multipurpose Refiectometer). Using this procedure, tests are conducted at temperatures of 80 F., 100 F., 120 F., 140 F., and 160 F. The resultant data, presented as percent whiteness increase, are as follows:

Whiteness increase percent Bleach mixture 80 F 100 F. 120 F. 140 F. 160 F.

Dichloro-2,4,6,8-tetrazabicyolo(3.3.0)octa-3,7-dione 19.6 22.8 24.2 25 7 27.8 2,4,6,8-tetrachloro-2,4,6,7-tetrazabicyclo (3.3.0) cote-3,7-

dione 25. 4 28. 0 30. 3 20. 5 32. 1

Part B being rotated on a turntable in a Whiteness increase (percent) Parts by Bleach mixture weight 160 F. F. F. F. F.

75 Dichloro 2,4,6,8tetrazabicyclo(3.3.0)octa-3,7-dione 25 2,4,6,8-tetrachloro-2,4,6,8-tet- 25.2 22.1 31.0 31.1 31.9

razabicyclo (3.3.0) octa-3,7 dione 50 Dichloro-2,4,G,8-tetrazabicyclo(8.3.0)octa-3,7-di0ne 50 2,4,6,8tetrachloro-2,4,6,8-tet- 25.3 27.6 32.0 34.0 35.6

razabicyclo (3.3.0) 00t3-3,7- dione EXAMPLE V Using 2,4,6,8-tetrachloro-2,4,6,8-tetrazabicyclo (3 .3 .0) octa-3,7-dione as a test fungicide spore germination tests on glass slides are conducted via the test tube dilution method adopted from the procedure wherein the test chemical, in aqueous formulations at concentrations of 1000, 100, 10 and 1.0 p.p.m. is tested for its ability to inhibit germination of spores from 7- to IO-day-old cultures of Alternarizz oleracea and Monz'lilzia fructicola. These concentrations refer to initial concentrations before diluting four volumes with one volume of spore stimulant and spore suspension.

Germination records are taken after 20 hours of incubation at 22 C. by counting 100 spores. The test compound is rated on its ability to inhibit germination of half of the spores, i.e., the so-called ED-50 value, in

EXAMPLE VI The tomato foliage disease test measures the ability of a test compound to protect tomato foliage against infection by the early blight fungus Alternaria solani and employs tomato plants 5 to ,7 inches high of the variety Bonny Best. Duplicate plants are sprayed with-100 m1. of the test formulation at 2000 and 400 p.p.m. (2000 or 400 p.p.m. 2,4,6,8 tetrachloro 2,4,6,8 tetrazabicyclo (3.3.0)octa 3,7 dione-5% acetone0.01% Triton X-balance water) at 40 lbs. air pressure While spray chamber.

After the spray deposit is dry, the treated plants and comparable untreated controls (sprayed with formulation less toxicant) are sprayed with a spore suspension containing approximately 20,000 corridia of Alternaria solani per ml. The atomizer used delivers 20 ml. in a 30-second exposure period. The plants are held in a saturated atmosphere for 24 hours at 70 F. for early blight to permit spore germination andinfection before removal to the greenhouse. After 2 to 4 days, lesion counts are made on the three uppermost fully expanded leaves. The data are converted to percentage disease control based on the number of lesions obtained on the control plants.

Using the above procedure, a 100% disease control is obtained at 2000 p.p.m. while 99% disease control is obtained at 400 p.p.m., thus indicating a high degree of fungicidal activity in protecting tomato foliage.

EXAMPLE v11 To illustrate nematocidal activity of compounds of this invention, composted greenhouse soil in gallon glazed V variety "Bonny 'Best.

cro'cks is infested with 3-5 gms. of knotted or galled tomato roots afflicted with root knot nematode (Meloidogyne sp.). Treatmentof an equivalent rate of 512 lbs. per acre (770 mg. per crock) is effected by mixing 2,4,6,8 tetrachloro-2,4,6,S-tetrazabicyclo(3.3.0)octa-3,7- dione intimately with the soil. An indicator crop of either squash or tomato is planted in the crooks 4 to 7 days after treatment and the degree of knotting or galling is used as an index of the nematocidal activity of the material. A rating system of for none to for severe infestation comparable to controls is used to report results of tests.

Using the above procedure, it 'is observed that a 0 phytotoxicity rating is obtained and a nematode infection of 0.5 is observed, this later rating in contrast to a nematode infestation rating of 4.7 for an untreated infested check sample.

EXAMPLE VIII Non-plant parasitic nematodes (Panagrellus redivivus) are exposed to 2,4,6,8-tetrachloro-2,4,6,S-tetrazabicyclo- (3.3.0)octa-3,7dione (1000 p.p.m. aqueous formulation) in small watch glasses (27 mm. dia. x 8 mm. deep) within a 9 cm. Petri dish, and results are recorded 24 hours after treatment. With the above procedure, a nematode mortality of 100% is observed.

EXAMPLE IX To indicate fungicidal activity of dichloro-2,4,6,8-tetrazabicyclo(3.3.0)octa-3,7-dione, spore germination tests on glass slides are conducted using this compound by employing the test chemical in aqueous formulations at concentrations of 1000, 100, 10 and 1.0 p.p.m. in tests to determine its ability to inhibit germination of spores EXAMPLE X 2,4,6,8 tetrachloro 2,4,6,8-tetrazabicyclo(3.3.l)non'a- 3,7-dione, spore germination tests on glass slides are conducted using this compound by employing the test chemical in aqueous formulations at concentrations of"1000,"

100, 10 and 1.0 p.p.m. in tests to determine its ability to inhibit germination of spores from 7- to 10-day-old cultures of 'Alte'rnaria oleracea and Monilinia jructicola; These concentrations refer to initial concentrations be fore diluting four 'volumes with 'onefvolum'e of spore stimulant and spore suspension. Germination records are taken a'fter20 hours of incubation at 22 C. by countmg 100 spores.

called ED-50 value in the testdrops. Using'the above procedure, an ED- SO value rating against the two organismsof 10 to 100 p.p.m. and 1 to '10 p.p.m., respectively, is observed, thus indicating a high degree of fungicidal activity. 7 V V r 'EXAMPLE XI The tomato foliage disease test measures the ability of a test compound to protect tomato foliage against infection by the early blight'fungus Alrernarza solani and the late blight fungus Phytopht'hora infestans. The meth- 5 to 7 inches high of the od employs tomato plants 7 Duplicate plants, one set for each test fungus, are sprayed withlOO. ml. of the test formulation 'at 2000and 400 p.p.m. (2000 or -400 pIp .m;*dichloro-' Ger-' To indicate fungicidal effectiveness of '1,5-dimethyl-.

The test compound is rated on its ability toinhibit germination of half of the spores, i.e., the somosphere for 24 hours at F. for early blight and 60' F. for late blight to permit spore germination and in- After 2 to fection before removal to the greenhouse. 4 days, lesion counts are made on' the three uppermost fully expanded leaves. The data are converted to per centage disease control based on the number of lesions obtained on the control plants. Using the above pro cedure, the percentage disease control of early blight at the two concentrations is 98% and 62%, respectively. Percentage disease control of the late blight at these concentrations is 100 and 99%, respectively.

EXAMPLE XII After the spray deposit is dry,'the treated plants and comparable untreated controls (sprayed with formulation less toxicant) are sprayed with a spore suspension containing approximately 20,000 conidia of Alternaria solani per ml. The atomizer used delivers 20 ml. in a 30-second exposure period. The plants are held in a saturated atmosphere for 24 hours at 70 F. for early blight to permit spore germination'and infection before removal to the greenhouse. After 2 to 4 days, lesion counts are made on the three uppermost fully expanded leaves. The data are converted to percentage disease control based on the number of lesions obtained on the control plants. Using the above procedure, a 100% disease control is observed at both concentrations employed.

EXAMPLE xnr Non-plant parasitic nematodes (Panagrellus redivivus) are exposed to dichloro-2,4,6,8-tetrazabicyclo(3.3.0)- octa-3,7-dione (1000 p.p.m. aqueous formulation) in smallwatch glasses, (27 mm. dia. x 8 mm. deep) within a 9 'cm. Petri dish and results are recorded 24 hours after treatment. 1 Using the above procedure,a nematode mortality of 100% is observed.

' EXAMPLE Xijv" phaseoli, Staphylococcus aureus and Escherichia coli in v the form of a bacterial suspension in a saline solution from potato-dextrose agar plates. 2 The tubes are then incubated for 4 hours at '30? C. Transfers are then made, j to sterile'broth with a standard 4 mm. loop and thethusj inoculated broth incubated for 48 hours at 37 Cawhen growth is rated as followsi A=no growth, B=slight, V C=moderate and D=heavy growth.' 7 r Using the above procedure, at the indicated concentrations, the following results are obtained:

Growth rating of 4 organisms 48 hrs. after a 4-hour exposure to V test compounds at 500 p.p.m. Bacterlcide Concentration, p.p.m. E. X. S. 1114- amylophasreus E. 0012 flora eoli 2,4,6,8-tetrachloro-2,4,6,8- 128 A A A A tetrazabicyclo(3.3.0)octa- 64 A A A A 3,7-dione 32 A A A B 1 16 A A A A 1 8 B A A A 128 A A A A Dichloro-2,4,6,8-tetrazabi- 64 O A A A cyclo (3.3.0)octa3,7-dione 32 O A A A 1 16 B A A A 1 8 B A A A 256 A A A A Roccal 2 64 C B B A 16 C B B O 128 A A A A Clorox 3 it: i i i l 8 A A A A Control D D D D 1 Test organism concentration is 256 p.p.m. 2 Roccal-benzalkonium chloride. 3 Clorox-aqueous solution of sodium hypochlorite.

EXAMPLE XV The following are illustrative specific bleaching and sanitizing formulations embodying the present invention and including 2,4,6,8-tetrachloro-2,4,6,8-tetrazabicyclo (3.3.0)octa-3,7-dione, 1,5-dimethyl-2,4,6,8-tetrachloro-2, 4,6,8-tetrazabicyclo(3.3.1)-nona 3,7 dione and/or dichloro-2,4,6,8-tetrazabicyclo(3.3.0)octa-3,7-dione.

BLEACHING AND 10 alkali-metal carbonates, silicates and phosphates and 2,4, 6,8-tetrachloro-2,4,6,8-tetrazabicyclo(3.3.0)octa-3,7-dione.

4. A disinfecting and bactericidal composition comprising a major proportion of an alkaline phosphate detergent and about 1% to 25% of a compound of the formula:

wherein R and R are alkyl groups; R R R and R are halogen; x, m, n, p and q are each numbers from to 1, inclusive.

5. A disinfecting and bactericidal composition comprising about to 50 parts of sodium sulfate, about 5 to 25 parts of monobasic sodium phosphate hydrate, about 5 to 60 parts of sodium tripolyphosphate, about 1 to 10 parts of an organic wetting agent and about 25 parts of a compound of the formula:

wherein R and R are alkyl groups; R R R and R SANITIZING FORMULATIONS ABIC DIE FIGH I .TKLM'N'OIPQIRIS TU N-chloro compound 25 25 25 25 255 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 Sodium sulfate 50 39 39 39 41 30 30 30 34 24 14 25 15 5 50 50 50 41 41 41 Monobasic sodium phosphate hydrate (NaH2P0;.HzO) 10 10 5 10 10 5 14 19 24 14 19 24 Sodium tripolyphosphate 14 25 14 25 30 35 60 40 50 60 10 5 10 5 Wetting agent (Di-Aqua) 1 1 1 1 1O 10 10 10 1 1 1 10 10 10 1 1 1 10 1O 1 Di-Aqua is a com mercially available alkyl aryl sulfonate, typically a mixture of sodium keryl benzene sulfonate (40% or 80% by weight), e.g., sodium dodecyl benzene sulfonate, balance sodium sulfate.

it is to be understood that although the invention has been described with specific reference to particular embodiments thereof, it is not to be so limited, since changes and alterations therein may be made which are Within the full intended scope of this invention as defined by the appended claims.

What is claimed is:

1. A composition of matter comprising a mixture of an alkaline material selected from the group consisting of alkali-metal carbonates, silicates and phosphates and a compound of the formula:

R4, R5 and R6 n, p and q are each numbers from are halogen; x, m, n, p and q are each numbers from 0 to 1, inclusive.

6. A bleach composition comprising an alkaline buffer selected from the group consisting of alkali-metal carbonates, silicates and phosphates and a mixture of two diiferent compounds of the general formula:

wherein R and R are alkyl groups; R R R and R are halogen; x, m, n, p and q are each numbers from 0 to 1, inclusive, said mixture containing 50% to 75% of one of the compounds and 50% to 25% of the second compound.

7. A bleach composition comprising an alkaline buffer selected from the group consisting of alkali-metal carbonates, silicates and phosphates and a synergistic mixture of 50% to 75% of dichloro-2,4,6,8-tetrazabicyclo- (3.3.0)octa-3,7-di0ne and 50% to 25 of 2,4,6,8-tetrachloro-Z,4,6,8-tetrazabicyclo(3.3.0)octa-3,7-dione.

8. The method of disinfecting and destroying bacteria which comprises contacting the material to be disinfected with the composition of claim 1.

9.The method of disinfecting and destroying bacteria 4 which comprises contactingthe material tobe disinfected with theco'rnposition of claim 2.

10. The method of disinfecting and destroying bacteriawhich comprises contacting the material to be disinfected with the composition of claim 3.

11. The method of disinfecting and destroying bacteria which comprises contacting the material to be disinfected with the composition of claim 4.

References Cited in the file of this patent UNITED STATES PATENTS UNITED STATES PATENT OFFICE CERTIFICATION 0F COECTIUN Patent No: 310191160 January 3O Frank B, Slezak et al.

It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 1 line 66 for "single" read singular line 71 for "verious" read various column 2, line 72, for "2a 1 13,0 read 2.0:l,0 column l0 lines 55 to 60 the formula should appear as shown below instead of as in the patent:

(H) -N c N (H) l-m I i I l-p O=C I C=O l (CI-I (H) N c N (H) Signed and Sealed this 3rd"day "of'Julyl'962"z.

C SEAL) Attest:

ERNEST W. SWIDER Attesting Officer DAVID L. LADD Commissioner of Patents UNITED STATES PATENT OFFICE CERTIFICATION OF CORRECTION Patent No: 3.0191160 January 30 1962 Frank B, Slezak et al9 It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below 7 Column l line 66 for "single" read singular line 71,, for "verious" read various column 2 line 72 for "2:. 121590 read 2.0:l.,0 column 10 lines 55 to 60 the formula should appear as shown below instead of as in 1 16 patent:

(11 m a) /(11 (11 (a) -i I\I (H) OZIC (3:0 (H) I N C N (H) l-n l-q Signed and sealed this 3rd day ofduly 19626 (SEAL) Attest:

ERNEST W. SW IDER Attesting Officer DAVID L. LADD Commissioner of Patents 

1. A COMPOSITION OF MATTER COMPRISING A MIXTURE OF AN ALKALINE MATERIAL SELECTED FROM THE GROUP CONSISTING OF ALKALI-METAL CARBONATES, SILICATES AND PHOSPHATES AND A COMPOUND OF THE FORMULA:
 8. THE METHOD OF DISINFECTING AND DESTROYING BACTERIA WHICH COMPRISES CONTACTING THE MATERIAL TO BE DISINFECTED WITH THE COMPOSITION OF CLAIM
 1. 